JP2015529556A - Selective catalytic deoxygenation of biomass and catalyst therefor - Google Patents

Abstract

The present invention relates to a new and effective pyrolysis catalyst adapted for use in biomass pyrolysis, the preparation of such a catalyst, and the addition of air, addition of molecular oxygen, and addition of molecular hydrogen and water. The use of such a catalyst in the pyrolysis of biomass, excluding the addition of such liquids, is provided. A catalyst is a layered HTC and related material impregnated with a specific pair of metals, and the impregnated layered HTC and related material is calcined at high temperature in air. [Selection] Figure 1

Description

  The present invention provides a new and effective pyrolysis catalyst adapted for use in biomass pyrolysis, the preparation of such a catalyst, and the addition of air, the addition of molecular oxygen, the addition of molecular hydrogen and / or water. To the use of such catalysts in the pyrolysis of biomass, excluding the addition of liquids such as

  Despite years of diligent research, there remains a problem of forming pyrolysis fluids rich in hydrocarbons and / or hydrocarbon precursors that effectively catalytically pyrolyze and selectively concentrate biomass. . In attempts to improve pyrolysis products and processes, it has been proposed to use low pyrolysis temperatures with or without the addition of water or hydrogen. In our laboratory, unfortunately, at least in the absence of water or hydrogen, the use of low temperatures can substantially increase the amount of carbon that is converted to coke, thereby resulting in a very low efficiency treatment for carbon content. Has been found. This also has a detrimental effect on the usefulness of pyrolysis processes for producing hydrocarbon-like transportation fuels due to the low yield of hydrocarbon-like products produced.

  It has now been found that pyrolysis deoxygenation can be catalytically concentrated, directed or directed in a specific selected direction during the pyrolysis of a suitable type of biomass. This likewise allows the formation of gaseous products (carbon monoxide, carbon dioxide and water) that are concentrated in various ways. In addition, pyrolytic oils can be produced that have improved properties such as, for example, low acidity, low oxygen content, reduced corrosivity, and the desired carbon / hydrogen ratio. As a result, less post-treatment of pyrolysis oil is required and better compatibility / miscibility with fossil fuels is achieved because the amount of oxygen-containing polar compounds in the pyrolysis oil is reduced.

The present invention provides, inter alia, a method for pyrolyzing solid state biomass material to produce pyrolysis oils with improved properties and mixtures of gaseous CO, CO ₂ and / or H ₂ O. Makes it possible to achieve these advantages. Such a method is
(I) under agitation in a pyrolysis reactor (A) particulate or finely divided solid biomass material that is untreated except for any drying and / or crushing;
(B) When loaded into the reactor (ie, just prior to loading): (1) a single pair of metals, (2) at least one oxide of each single pair of metals, or (3) (a) a single pair At least one calcined hydrotalcite or hydrotalcite impregnated or carrying at least one oxide of one or both of the metals and (b) at least one free metal of one or both of a single pair of metals Impregnated or doped solid state calcination comprising, consisting essentially of, or consisting of a calcination product comprising such compounds, layered dihydroxides, anionic clays, or mixtures of two or more thereof A pyrolysis catalyst, wherein the calcined product is selected in the presence of free oxygen (eg air or oxygen and nitrogen, neon, argon or krypton At least one pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide impregnated with or carrying a salt of said pair of metals with a mixture of at least one inert gas) , An anionic clay, or a mixture of two or more thereof, and a single pair of metals of (1), (2), or (3) is composed of the following groups: Ca and Ce, Ca and Cu, Selected from Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Ce and Fe, Ce and Ni, Ce and Y, Cu and Nb, Fe and Y, Mo and Zn, Mn and Y, Ni and Y And (C) forming a mixture by contacting the solid state particulate heat medium;
(II) In the pyrolysis reactor, excluding (without) the addition of air, molecular oxygen, molecular hydrogen, and / or the addition of a liquid diluent or carrier such as water. At least one portion of the mixture of (I) at a temperature of one or more above about 500 ° C. rapidly or instantaneously pyrolyzing, thereby forming a fluid pyrolysis product. In other words, none of the following is added: (i) liquid diluent such as air, (ii) molecular oxygen, (iii) molecular hydrogen, (iv) water.
Each such method using the individual catalysts identified in (I) and (B) above constitutes an individual embodiment of the present invention. The above-described methods may include (1) pyrolysis oil of improved quality and / or rich hydrocarbon content, and / or (2) carbon monoxide or carbon dioxide or water, or carbon monoxide, carbon dioxide, water Two or all of the mixtures allow the formation of a pyrolysis product of a fluid containing a selectively rich gas phase.

  As used herein, including the claims, the term “rehydrated” in the phrase “rehydrated, impregnated or doped solid state calcined pyrolysis catalyst” refers to the catalyst composition. It means that rehydration is performed to activate the catalyst at a suitable stage of catalyst preparation prior to the final calcination step to complete formation.

  Whenever the word “catalyst” is used, the material referred to should be considered a catalyst precursor because in use it (“catalyst”) is exposed to other materials under various reaction conditions. It should be understood and recognized correctly. Thus, when charged to the reactor, it (“catalyst”) is impregnated with or carried by component (1), (2) or (3) of (B) above or at least one hydrotalcite It comprises, consists essentially of, or consists of a calcined product formed from a hydrotalcite-like compound, a layered dihydroxide, an anionic clay, or a mixture of two or more thereof ("catalyst") May undergo chemical changes under certain reaction conditions present in the pyrolysis reactor.

The terms “hydrotalcite”, “hydrotalcite-like compound”, “layered dihydroxide” and “anionic clay” are considered in the art as alternative expressions for well-recognized categories of products . Indeed, various other names such as layered double hydroxides and anionic clays have also been applied to these materials in the art. In this context, Rivers, V.M. Ed. “Layered Double Hydroxides: Present and Future”, Nova Science Publishers, Inc. , New York, 2001, Chapter 1. Because these materials are well known in the art and are well described and characterized, anyone who wants more information about such materials can use natural and synthetic materials useful in the practice of the present invention. Have enough source material available to understand. Other useful sources of such information are F.I. Cavani et al., “Hydroitalite-Type Anionic Clays: Preparation, Properties and Applications”, Catalysis Today, 11 (1991) Elvis Science Publishers B. V. Amsterdam; and J.P. Besse et al., Anionic Clays: Trends in Pillar Chemistry, it's Synthesis and Microporous Solids (1992), 2, 108, editors: I. Occelli, H.C. E. Robson, Van Nostrand Reinhold, N.A. Y. It is. For convenience, the term “hydrotalcite”, “hydrotalcite-like compound” or “HTC”, whether singular or plural, is used in this document to refer to the entire category of substance (hydrotalcite, hydrotalcite-like compound). , Layered dihydroxide, anionic clay). To the extent that these materials may differ, mixtures thereof, if any, may be used. Synthetic "HTC" is generally preferred, but natural and synthetic hydrotalcites are included in this category. More preferably, the HTC used is a synthetic hydrotalcite in which the two metals forming the oxide are magnesium and aluminum.

  In carrying out the pyrolysis method mentioned above, the operation is carried out under rapid or instantaneous pyrolysis conditions. Thus, the temperature rises from room temperature at a rate of at least 100 ° C. per second, exceeding 500 ° C., and preferably not higher than about 650 ° C. Another way to achieve rapid or instantaneous pyrolysis is that the average residence time of the pyrolysis products in the pyrolysis reactor is very short, usually 30 seconds or less, preferably 20 seconds or less, more preferably The operation is to be 10 seconds or less. Depending on the reactor design and the auxiliary equipment employed, even shorter average residence times are possible. Usually, pyrolysis temperatures above about 700 ° C. are rarely used. Desirably, the maximum pyrolysis temperature used in the present invention is about 650 ° C, preferably about 575 ° C or less. A desirable and preferred temperature range is from about 500 ° C. to about 600 ° C. at substantially normal pressure and in the range of about 510 ° C. to about 575 ° C. Reactors that can be used include fluidized bed reactors, Auger reactors, foam reactors and the like. Of these, fluidized bed reactors have been found to provide very good performance. If desired, the pyrolysis product can be cooled with a suitable liquid, such as water, immediately after removal from the pyrolysis reactor.

  In the preferred mode of operation, the pyrolysis is carried out at substantially atmospheric pressure and is solid, for example, in a stream of an inert anhydrous carrier gas such as dry nitrogen or other inert anhydrous carrier gas such as neon, argon or krypton. The biomass material in the state is brought into the pyrolysis reactor.

  The amount of the additional pair of two metals (calcined as a metal) as distinguished from the amount of HTC in the resulting catalyst composition after calcination can vary, but is usually from about 1 to about 10 In the range of wt%, preferably in the range of 4 to about 9 wt%, these ratios are based on the total weight of the fired composition. The atomic ratio of the additional pair of two metals (fired again as metal) to each other in the impregnated and calcined HTC catalyst composition is usually in the range of about 1:15 to about 15: 1, preferably about It is in the range of 1: 7 to about 7: 1, more preferably in the range of about 1: 3 to about 3: 1.

  As used throughout this document, the terms “solid state biomass”, “solid biomass”, “biomass” and “biomass material” may be used to refer to “solid state biomass material”.

  Although various types of solid state biomass material can be used, lignocellulosic biomass is a preferred type of biomass material for use in the pyrolysis process of the present invention. A typical lignocellulosic biomass contains approximately 45% by weight carbon, approximately 6% hydrogen and approximately 49% oxygen, although other similar lignocellulosic biomass materials are also representative and are in use. It seems preferable.

  Of the solid-state particulate heat media that can be used (sometimes referred to as heat transfer agents), sand (eg, silica sand) is abundant and very effective. For example, other materials such as volcanic ash, crushed rock, crushed concrete and the like can be used if desired. Mixtures of different solid state particulate heating media can be used if desired.

In accordance with another embodiment of the present invention, the pyrolysis of biomass material in the solid state is selectively directed towards the formation of a hydrocarbon-rich pyrolysis oil, heat with oxygenated products and / or improved properties. A solid state pyrolysis catalyst composition adapted to selectively direct away from formation of cracked oil therein; and / or one or more of CO, CO ₂ and / or H ₂ O is selectively Abundant pyrolysis gas formation is provided. These new catalysts in the form when loaded into the reactor (ie just before loading) are the following groups: Ca and Ce, Ca and Cu, C
a and Fe, Ca and Mn, Ca and Y, Ca and Zn, Ce and Fe, Ce and Ni, Ce and Y, Cu and Nb, Fe and Y, Mo and Zn, Mn and Y, Ni and Y At least one pre-calcined hydrotalcite or hydrotalcite-like compound impregnated or carrying an inorganic salt, preferably an inorganic salt, layered dihydroxide, anionic clay, or two or more thereof Comprising, consisting essentially of, or consisting of a calcined catalyst formed from at least one catalyst precursor comprising, consisting essentially of, or consisting of. Calcination of the catalyst precursor is performed by free oxygen (eg, air or oxygen and nitrogen, neon, argon or krypton) such that at least a portion of one or both of the metal pair is converted to an oxide. In the presence of a mixture of at least one inert gas selected from: Each calcined catalyst referred to in this paragraph constitutes an individual embodiment of the present invention.

The catalyst of the present invention is formed from an HTC usually represented by the general formula: [M ^II _(1-x) M ^III _x (OH) ₂ ] ^{x +} [A ^II− ] _{x / n} · mH ₂ O, , M ^II is a divalent metal such as Mg ²⁺ , Co ²⁺ , Cu ²⁺ , Ni ²⁺ , Zn ²⁺ , and M ^III is Al ³⁺ , Cr ³⁺ , Ga ³⁺ , Fe ³⁺ ; A ^II− is an organic ion and / or an inorganic ion. See, for example, Rivers, V .; , Editor. Layered Double Hydroxides: Present and Future, Nova Science Publishers, Inc. , New York, 2001; Monzon et al., Chapter II of what is entitled "Hydrogenation Catalysts with Mixed Oxides Prepared from LDH"; Valente et al.

Yet another embodiment of the present invention excludes the addition of liquids such as air, molecular oxygen, molecular hydrogen or water, and is particulate or fine that is untreated except for any drying and / or crushing. A method of preparing a catalyst composition adapted to produce a pyrolysis product from a separated solid state biomass material. The method of preparing the catalyst composition includes:
(A) a pair of selected metals dissolved, viewed individually or collectively, of such a solution, which may be the same or different, an evaporable solvent, preferably water Producing or providing one or more solutions that provide a solvent (usually one solution or two separate solutions) (the metal contents of the one or more solutions are Ca and Ce, Ca and Cu, Ca And Fe, Ca and Mn, Ca and Y, Ca and Zn, Ce and Fe, Ce and Ni, Ce and Y, Cu and Nb, Fe and Y, Mo and Zn, Mn and Y, Ni and Y Selected molten metal pair), and
(B) Powdered or particulate hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anion by initial wetting using one or more of the solutions of (A) above Impregnated with a clay, or a mixture of two or more thereof to form a wet mixture, the resulting wet mixture is dried to form a product mixture, and then free oxygen (eg, air or oxygen and nitrogen, neon) Calcining the product mixture in the presence of a mixture of at least one inert gas selected from argon or krypton). This calcination of the dried mixture is performed with the optional pair of metals together with the optional co-existence of free metal corresponding to one or both of the dissolved metal pairs of the one or more solutions of (A) above. Is converted to such a metal oxide.
Each of the above methods for preparing individual catalyst precursors as in (A) above constitutes an individual embodiment of the present invention. In connection with excluding the addition of liquids such as air, molecular oxygen, molecular hydrogen or water, accidental quantities of liquids such as air, molecular oxygen, molecular hydrogen or water are, for example, It is understood that it can be derived from biomass material.

  A further embodiment of the invention is a method for converting solid state biomass material to at least:

(AA) One or more fluid hydrocarbon products, methods, can be used to process a particulate or finely divided solid state biomass material that is untreated except for any drying and / or crushing, under rapid or instantaneous operating conditions. In a reactor operating at a temperature above about 500 ° C., said reactor being (1) when first introduced into the reactor,
(A) of a solution, such as water, preferably an evaporable solvent, preferably water, which may be the same as or different from the selected pair of metals, either individually or collectively. Producing or providing one or more solutions that provide a solvent (usually one solution or two separate solutions) (the metal contents of the one or more solutions are Ca and Ce, Ca and Cu, Ca And Fe, Ca and Mn, Ca and Y, Ca and Zn, Ce and Fe, Ce and Ni, Ce and Y, Cu and Nb, Fe and Y, Mo and Zn, Mn and Y, Ni and Y Selected molten metal pair), and
(B) Powdered or particulate hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anion by initial wetting using one or more of the solutions of (A) above An impregnated clay, or a mixture of two or more thereof to form a wet mixture, the wet mixture is dried to form a product mixture, and then free oxygen (eg, air or oxygen and nitrogen, neon, argon or Calcined pyrolysis catalyst which is a catalyst formed by a process comprising calcining a product mixture in the presence of a mixture of at least one inert gas selected from krypton) and (2) solid state particles Containing a fluidized mixture with a heating medium,
In doing so, the pyrolysis is carried out excluding the addition of air, the addition of molecular oxygen, the addition of molecular hydrogen and / or the addition of a liquid diluent or carrier such as water. Thereby, a pyrolysis product of the fluid is formed.

  (AB) The metal pair is selected from Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo and Zn, and Mn and Y ( Method AA).

  (AC) The method of (AB), wherein the pair of metals is selected from Ca and Cu and Ca and Fe.

  (AD) The pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof is magnesium and aluminum (AA), (AB) ) Or (AC).

  (AE) The rapid or instantaneous operating conditions comprise a temperature substantially above 500 ° C. to about 650 ° C. at atmospheric pressure, and the biomass material is an inert anhydrous carrier gas, preferably nitrogen, argon, The average particle size of the calcined pyrolysis catalyst as loaded into a pyrolysis reactor with neon or krypton or a mixture of two or more thereof, wherein the solid state particulate heating medium is sand and loaded into the reactor is about In the range of 40 to about 400 microns, preferably in the range of about 50 to about 150 microns, and the calcined pyrolysis catalyst as loaded in the pyrolysis reactor has been activated by rehydration, The method of any one of (AA), (AB), or (AC), wherein the average residence time in the vessel is 30 seconds or less, preferably 20 seconds or less, and more preferably 10 seconds or less.

(AF) The metal contained in the pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof is magnesium and aluminum, The instantaneous operating conditions comprise a temperature substantially above 500 ° C. to about 650 ° C. at atmospheric pressure, and the biomass material is an inert anhydrous carrier gas, preferably nitrogen, argon, neon or krypton or more The solid state particulate heating medium is sand and the average particle size of the calcined pyrolysis catalyst as loaded in the reactor is in the range of about 40 to about 400 microns. The calcined pyrolysis catalyst, preferably in the range of about 50 to about 150 microns, as loaded in the pyrolysis reactor, has been activated by rehydration. The average residence time in the pyrolysis reactor is 30 seconds or less, preferably 20 seconds or less, more preferably not more than 10 seconds (AA), one of the methods of (AB) or (AC).

  For convenience, a catalyst composed of HTC that is preferably impregnated with a pair of metals and / or metal salts and calcined at one or more suitable high temperatures is referred to herein as a “bimetallic catalyst of the invention”. Sometimes called. It should be understood that the term “bimetallic catalyst of the present invention” does not mean that two different metals or different metal pairs are the only metal form. Instead, this term refers to the bimetallic catalyst of the present invention containing one or more suitable elevated temperatures in the atmosphere or oxygen prior to use, such as nitrogen, argon, neon or krypton. Is fired in an inert gas such as when there are two metal elements present in a metal pair when loaded into the reactor (ie, just prior to loading), one or both of which are partially Meaning that it may be in the form of one or more oxides in whole or in total. In short, the free metal of the pair and / or one or more oxides of one or both of such metals can be present as a coating impregnated with the bimetallic catalyst of the present invention.

  In each of the above embodiments, the average particle size of the bimetallic catalyst of the present invention desirably falls in the range of about 40 to about 400 microns, preferably in the range of about 50 to about 150 microns.

  The calcination temperature used to form the bimetallic catalyst of the present invention can vary. Usually, a suitable firing temperature is in the range of about 550 ° C to about 800 ° C. A preferred temperature is in the range of about 575 ° C to about 700 ° C. More preferred is a temperature in the range of about 575 ° C to about 625 ° C, for example 600 ° C.

  The above calcination temperature is obtained by using hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof used to form the bimetallic catalyst of the present invention. It is also suitable for use in pre-baking.

  These and other features, embodiments and / or advantages will become more apparent from the following description, the appended claims and the accompanying drawings.

Using a laboratory-level method of catalyst preparation, impregnation or doping with a metal pair for drying and calcination for the effectiveness in producing CO and CO ₂ via rapid pyrolysis at 515 ° C. It is a bar graph which shows the result obtained in the thermal decomposition experiment which investigated various HTC which carried out. Using catalyst preparation method A or B, the effectiveness of producing water by pyrolysis was obtained by pyrolysis experiments in which various HTCs that were impregnated or doped with metal pairs, dried and then calcined were examined. It is a bar graph which shows the obtained result. A preferred semi-allowable that allows a rapid assessment of the performance of a fluidizable catalyst composition with respect to the acidity of the pyrolysis oil product produced using such a catalyst composition in accordance with the present invention and the removal of oxygen therefrom. It is a side view of the cross section of the performance test apparatus of an adiabatic fluidized bed.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides, inter alia, solid state biomass material (eg, lignocellulosic biomass or other biomass material, particularly from terrestrial sources, and provides a substantial amount of hydrocarbons upon pyrolysis. Products rich in hydrocarbons and at least one, preferably more than one hydrocarbon precursor (ie, carbon monoxide, carbon dioxide and / or water) in a single reaction step. A method of converting solid state biomass to be converted to is provided. This includes the addition of air, the addition of molecular oxygen, the addition of molecular hydrogen, the addition of molecular ozone and the addition of liquids such as water at a high reaction temperature suitable for one or more using the catalyst of the present invention. Is accompanied by the pyrolysis of a suitable solid state biomass material, especially rapid pyrolysis.

  A wide range of biomass feedstocks of various types, sizes and moisture contents can be utilized in the practice of the present invention. Solid biomass materials include fast-growing timber (eg, willows and poplars), timber harvest residue or forestry waste, coniferous chips, hardwood chips, tree branches, tree stumps, leaves, bark, sawdust, Nonstandard paper pulp, agricultural waste, corn, corn stover, wheat straw, rice bran, sugarcane pomace, switchgrass, municipal waste, commercial waste, grape pomace, almond shell, pecan shell, coconut shell, Mention may be made of one or more substances selected from coffee grounds, grass pellets, hay pellets, timber pellets, cardboard and paper. Cellulosic biomass materials can be used as well. However, it has been found that such materials tend to form sticky residues during pyrolysis. Therefore, when using cellulosic biomass materials, careful temperature control and frequent cleaning of related equipment such as pyrolysis reactors and agitators are recommended. Generally speaking, lignocellulosic biomass materials and similar materials that are capable of providing substantial amounts of hydrocarbons by pyrolysis are preferred for use. Such materials can be processed in batches, semi-batches or continuously as desired.

  In an alternative embodiment, cellulosic biomass material is formed by land plants. Terrestrial plants have practically no exception, and form a combination of lignin and cellulose, commonly called lignocellulosic biomass. Although food crops can be used for use in the process of the present invention, it is economically and ethically mentioned to use energy crop material, agricultural waste or forestry waste. Examples of suitable energy crop materials include switchgrass and fast growing timber such as willow and poplar.

  The optional pretreatment of the solid state biomass material selected according to the present invention is limited to two types of pretreatment. One such pretreatment is to predry the biomass material prior to use in pyrolysis. This may involve the use of heat application, a suitable length of time, storage at a suitable temperature, spray drying or other similar air drying methods. Another pretreatment is to reduce the size of the biomass material prior to use in pyrolysis. This usually involves suitable mechanical processing such as milling, grinding, kneading, chopping, sawing, or other physical methods of crushing, or combinations thereof.

  As mentioned above, the catalyst of the present invention used to achieve pyrolysis is one or more powdered or particulate HTCs, which, when introduced into the pyrolysis vessel, are made of certain metals. It carries and is doped with one or more oxide coatings of one or both of the pairs and / or metal pairs.

  The primary function of the catalyst system used in accordance with the present invention with selected suitable solid state biomass material is to catalytically concentrate, direct or induce pyrolytic deoxygenation in a particular selected direction, Thereby, advantageous results are obtained in the heat treatment or in the quality of the fluid products (gas and liquid) formed in the treatment or both.

Used in all of the pyrolysis processes of the present invention, in all of the bimetallic catalysts of the present invention and in all of the processes of preparing the bimetallic catalysts of the present invention, to impregnate or dope the pre-fired HTC. Preferred pairs of additional metal components are the following nine individual metal pairs: Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo and Zn , And water-soluble compounds of Mn and Y (for example, salts, oxides or hydroxides). These bimetallic catalysts of the present invention are not only formed by impregnation of the substrate with an additional component (usually a salt) of the desired paired metal, but the impregnated substrate is then calcined to produce the metal and / or Or form a metal oxide catalyst surface, but the substrate is
(A) milling or otherwise crushing a physical mixture of a divalent metal compound and a trivalent metal compound;
(B) firing the milled or otherwise crushed physical mixture at a temperature in the range of 200-800 ° C;
(C) pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anion formed by a method comprising rehydrating the calcined mixture with an aqueous suspension Clay, or a mixture of two or more thereof, wherein an additional pair is present in the physical mixture and / or the aqueous suspension of step (c).
This method, useful for activating catalyst compositions in very small particle form, but without the use of certain additional combinations of the present invention, is disclosed in the US published patent of Jone et al., Published Feb. 7, 2008. Application No. US2008 / 0032884. For convenience, this process involving steps (a), (b) and (c) may be referred to hereinafter as the “catalyst activation process”. In this method, the term “physical mixture” refers to a mixture of compounds of (a) in a dry or aqueous state in which none of the compounds react with each other to a significant extent prior to calcination. Thus, the physical mixture may, over time, form a hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof that is pre-fired before firing. Absent.

  Thus, a bimetallic catalyst having any of the nine metal pairs mentioned in the immediately preceding paragraph has a surface impregnated with the desired metal and / or metal oxide, preferably as described in the immediately preceding paragraph. It is also activated by rehydration according to the catalyst activation method. More preferably, the metal contents of these pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof are magnesium and aluminum.

Description of Catalyst Preparation Procedures To illustrate the preferred procedure for preparing the bimetallic catalyst of the present invention, three different catalyst preparation methods were employed. Two such methods involved robotic plate impregnation using robotic instruments.

  In the first such method (hereinafter sometimes referred to as Catalyst Preparation Method A), Mg / Al / HTC powder (125-400 microns) was deposited on the plate. The required amount of impregnation solution in the vial is spread across the surface of the supported catalyst (HTC) in the form of a total of 49 droplets. The catalyst was then left with the impregnation solution for 30 minutes. The wet powder was mixed well and then calcined in air at 600 ° C. for 90 minutes with a temperature ramp of 5 ° C. per minute. The impregnation solution used in this operation was a metal nitrate using two metals as metal oxide precursors in the solution used for impregnation with the contents of the binary metal.

  The second method (hereinafter sometimes referred to as Catalyst Preparation Method B) involved robotic shaking impregnation using a commercial instrument manufactured for this purpose. In this method, 1.6 g of HTC was placed in a test tube. The required amount of one of the two metal precursors and / or metal oxide precursors was added along with the amount of water calculated using the pore volume of the HTC. Impregnation was started according to the initial wetting method using a robotic instrument in rotation / vibration mode. The resulting product was dried in a test tube at 120 ° C. for 1 hour. This procedure was repeated using a second metal and / or metal oxide precursor. After drying, the dried product was then calcined at 600 ° C. for 90 minutes with a temperature ramp of 5 ° C. per minute.

For the preparation of larger laboratory level catalysts, the following third method (hereinafter Method C) is used.
(Sometimes referred to as “laboratory method”) was used for impregnation and catalyst formation. Each preparation provided about 60 g of catalyst. About 120 g of sieved HTC was placed in a larger flask. The impregnation solution is formed by mixing the required amount of the first metal and / or metal oxide precursor with the minimum amount of water calculated from the pore volume of the HTC and then shaking the wet mixture. Followed by an initial wetting with an impregnating solution containing, followed by drying at 100 ° C. for 5 hours. This process was repeated for impregnation with a second precursor to prepare a mixture of two metal and / or metal oxide precursors. After the second drying, baking was performed at 600 ° C. As mentioned before, especially additional pairs are from Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo and Zn, and Mn and Y. If selected, the catalyst activation method described above is preferred in forming a pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof. Is used. Another advantage of using a catalyst activation method is that the milling or other crushing process used therein is a catalyst with a desirably small particle size, usually in the range of 40-400 microns, preferably in the range of 50-150 microns. Is to provide. For the preparation of even larger catalysts, conventional large impregnation and / or dope catalyst preparation procedures are known in the art and can be employed.

Catalyst Testing Procedure The results shown in FIG. 1 show that the biomass desorption of 3 g of particulate untreated lignocellulosic biomass with nitrogen gas flow at the top of a rapid pyrolysis fluidized bed reactor (see FIG. 3). Obtained by use of oxygen experiments. The fluidized bed consisted of a mixture of catalyst (12 g) and sand (36 g) in a weight ratio of 25 wt% bimetallic catalyst of the present invention and 75% sand. The fluidized bed temperature was maintained at about 515 ° C. at substantially normal pressure. The average residence time was less than 30 seconds.

The results shown in FIG. 2 are prepared using Catalyst Preparation Method A for all reported catalysts except for the following: lignocellulosic biomass (10 mg) and Ca / Nb / HTC catalyst prepared by Catalyst Preparation Method B. Obtained by use of biomass deoxygenation experiments conducted as in 10 mg of bimetallic catalyst. Each catalyst was prepared to provide a 1: 1 weight ratio of the metal target. The weight ratio of biomass to catalyst was 1: 1 (10 mg each). These mixtures were rapidly heated to 500 ° C. in a thermogravimetric analysis (TGA) cup in nitrogen (N ₂ ) all at a flow rate of 80 mL / min. Through the piping traced at 120 ° C., the formed pyrolysis vapor was passed through a Fourier transform infrared spectroscopic cell (FTIR) (capacity 15 mL, with KBr window heated to 150 ° C.), after which the FTIR spectrum was recorded: 1 spectrum / 2 seconds interval (consisting of 5 scans with a resolution of 0.5 cm ^-1 ). All reported spectra were corrected for biomass content. After normalized to the amount of biomass, in specific ranges 2244～2142Cm ^-1 to C = O vibration at carbon monoxide in the range of specific 2392～2258Cm ^-1 to C = O vibration at carbon dioxide , And the integrated peak areas for specific vibrations in the range of 3856 to 3853 cm ⁻¹ specific for OH vibrations in the water molecules formed.

FIG. 3 shows a cross-sectional side view of a preferred semi-insulated fluidized bed performance test apparatus. The apparatus includes a reactor 1, a product reservoir 2 and a gas bag 3. The reactor 1 has a biomass supply line 4, a heat medium supply line 5, a thermoelectric thermometer 6, a dipleg 7, and a nitrogen gas (N ₂ ) inlet.

The pyrolysis gas is analyzed by gas chromatography, and the yields of CO and CO ₂ are quantified as% by weight with respect to the feed rate (wet basis). The liquid (pyrolytic oil) is homogenized by dilution with tetrahydrofuran (THF). The homogenized liquid is analyzed for water content and acidity. The total yield of water found in the pyrolysis oil (corrected for THF dilution) is determined by standard Karl-Fischer titration and reported as weight percent relative to feed (wet basis). Acidity is reported as mg KOH per gram of liquid product at equivalent time points in the titration curve.

式中、
Ｏ_除去は、除去された酸素の重量％である（供給量における酸素を基にした重量％）
Ｍ_O：Ｏのモル質量＝１５．９９９（ｇ／モル）
Ｘ_CO：ＣＯの収率（供給量に対する重量％）
Ｍ_CO：ＣＯのモル質量＝２８．０１（ｇ／モル）
Ｘ_CO2：ＣＯ₂収率（供給量に対する重量％）
Ｍ_CO2：ＣＯ₂のモル質量＝４４．０１（ｇ／モル）
Ｘ_H2O：Ｈ₂Ｏの収率（供給量に対する重量％）
Ｍ_H2O：Ｈ₂Ｏのモル質量＝１８．０２（ｇ／モル）
Ｏ_供給：４９重量％がリグノセルロース系の供給量である供給されたバイオマスにおける酸素含量（重量％） Oxygen removal (from biomass feed) achieved by such pyrolysis experiments is expressed in the following way:

Where
O _removal is the weight percent of oxygen removed (weight percent based on oxygen in the feed rate).
M _O : Molar mass of O = 15.999 (g / mol)
X _CO : CO yield (% by weight with respect to the supply amount)
M _CO : molar mass of CO = 28.01 (g / mol)
X _CO2 : CO ₂ yield (% by weight with respect to the supply amount)
M _CO2 : Mole mass of CO ₂ = 44.01 (g / mol)
X _H2O: H ₂ O yield (wt% with respect to the supply amount)
M _H2O : Molar mass of H ₂ O = 18.02 (g / mol)
O _supply : Oxygen content (wt%) in supplied biomass where 49 wt% is the lignocellulosic supply

  The following examples illustrate various individual embodiments of the present invention. These examples are not intended to limit the invention to only the embodiments described in these examples. In these examples, the term HTC refers to a hydrotalcite or hydrotalcite-like compound in which the two hydroxide metals are Mg and Al. Such HTCs are impregnated with two different additional metal compounds in one or two steps and then calcined once or twice depending on the preparation method used. Using Ca and Cu as examples of impregnating compound metals used, the final calcined product derived from impregnation of HTC with this pair of additional metal compounds will usually have a slight chemical structure. It is called Ca / Cu / HTC despite containing oxide with metal. In all cases, the catalyst synthesis used impregnated compounds in each amount targeted to provide the metal in a 1: 1 weight ratio.

Examples 1-7
Seven different bimetallic catalysts of the present invention in an amount to produce the bimetallic catalyst of the present invention using an aqueous solution of Mg / Al / HTC and two different water soluble metal salts using catalyst-like method C Was prepared. The HTC used was pre-fired at 550 ° C. for 1 hour and held in a desiccator to avoid interaction with moisture and CO ₂ . The impregnation was carried out using the well-known initial wetting method with selected pairs of nitrates, ammonium salts and / or oxalates of additional metals. During firing at 600 ° C. in air or in an inert gas containing free oxygen as mentioned above, the presence of a part of one or both of the free metals cannot be ruled out completely. Is converted to a metal oxide. After the impregnated or doped HTC was calcined and activated by hydration, it was kept under inert conditions such as a desiccator to avoid interaction with moisture and gases such as CO ₂ . The seven calcined catalysts were then individually evaluated for performance in the laboratory-level pyrolysis apparatus depicted schematically in FIG. In all individual pyrolysis runs, 3 g of biomass at room temperature was fed to the top of the catalyst fluidized bed preheated to 515 ° C. The fluidized bed consisted of 12 g of the bimetallic catalyst of the present invention together with 36 g of sand. A 3 bar nitrogen purge was used to achieve introduction of the solid feed into the fluidized bed via the feed prepreg. After a rapid pyrolysis residence time of less than 30 seconds, the fluidized bed was flushed with nitrogen. During operation, the liquid product was concentrated and collected in a product reservoir equipped with a cold trap. Pyrolysis gas and nitrogen were collected in a gas bag. The pyrolysis gas was analyzed using gas chromatography. The liquid product was subjected to acidity, water measurement and FTIR or GC-MS analysis. The spent catalyst was analyzed for coke by burning the catalyst. The actual amount of coke measured represents the sum of both coke and carbide (non-converted biomass) in the catalyst. As a control, an experiment was conducted using only sand, and another experiment was conducted using only calcined HTC.

  Further details regarding Examples 1-7 are summarized in Table 1. The amount of metal in the catalyst was determined by using an inductively coupled plasma (ICP) method.

When examined under identical conditions, the COx (x of CO ₂ zeolite ZSM-5 is 10.2 wt% CO and 8.7% by weight of (wet basis) (wet basis) is usually 1 or 2 It is interesting to mention that it produces a distribution. Therefore, this well-known extensively investigated zeolite catalyst produced a COx distribution containing a large amount of toxic carbon monoxide. In marked contrast, the practice of the present invention allows the formation of COx distributions containing large amounts of carbon dioxide.

Examples 8-11
Using catalyst preparation method A or catalyst preparation method B, respectively, an aqueous solution of Mg / Al / HTC and two different water-soluble metal salts is used to produce the bimetallic catalyst of the present invention in an amount of 4 of the present invention. Two different bimetallic catalysts were prepared. These catalysts were Ca / Cu / HTC, Ce / Y / HTC, Cu / Nb / HTC and Ni / Y / HTC. The additional metal salts used to make the catalyst and the weight and atomic ratios of the metal pair used to make the catalyst are shown in Table 2. The four calcined catalysts were then individually evaluated for performance. In these operations, the biomass deoxygenation experiments consisted of the following: catalyst preparation method A for all reported catalysts except for lignocellulosic biomass (10 mg) and the Ca / Nb / HTC catalyst prepared by catalyst preparation method B. As 10 mg of the bimetallic catalyst prepared with. Each catalyst was prepared to provide a 1: 1 weight ratio of the metal target. The weight ratio of biomass to catalyst was 1: 1. These mixtures were rapidly heated to 500 ° C. in a thermogravimetric analysis (TGA) cup in nitrogen (N ₂ ) all at a flow rate of 80 mL / min. Through the piping traced at 120 ° C., the formed pyrolysis vapor was passed through a Fourier transform infrared spectroscopic cell (FTIR) (capacity 15 mL, with KBr window heated to 150 ° C.), after which the FTIR spectrum was recorded: 1 spectrum / 2 seconds interval (consisting of 5 scans with a resolution of 0.5 cm ^-1 ). All reported spectra were corrected for biomass content. After normalizing to the amount of biomass, the integrated peak areas shown in Table 2 were compared for specific vibrations in the range of 3856 to 3853 cm ⁻¹ specific for OH vibrations in the water molecules formed. . Further, thirteen other biomass deoxygenation experiments were similarly conducted using metals other than the metals of the four binary metal catalysts of the present invention. In one group, nine tests were performed including the Ca / Cu / HTC and Cu / Nb / HTC of the present invention and seven other copper bimetallic catalysts not of the present invention. Seven bimetallic catalysts that are not of the present invention are represented by the formula Cu / M / HTC, where M is each of seven different metals other than calcium and niobium, one of these other metals being Alkali metal (Li). In the other groups, eight tests involving Ce / Y / HTC and Ni / Y / HTC of the present invention were similarly performed. In this group, six bimetallic catalysts not according to the present invention are represented by the formula Y / M / HTC, where M is each of six different metals other than cesium and nickel, One is alkali metal (Li).

  Further details regarding Examples 8-11 are summarized in Table 2.

Examples 12-13
Using catalyst preparation method A, the pre-calcined Mg / Al / HTC and an aqueous solution of two different water-soluble metal salts are used to produce the two different two-metal catalysts of the present invention in an amount to produce the bimetallic catalyst of the present invention. An original metal catalyst was prepared. These catalysts were Ce / Fe / HTC and Ce / Ni / HTC. Table 3 shows the additional metal salts used to make the catalyst and the weight and atomic ratios of the metal pair used to make the catalyst. The two calcined catalysts were then individually evaluated for performance. In these operations, biomass deoxygenation experiments were performed as follows: lignocellulosic biomass (10 mg) and 10 mg bimetallic catalyst prepared using Catalyst Preparation Method A for both catalysts. Each catalyst was prepared to provide a 1: 1 weight ratio of the metal target. The weight ratio of biomass to catalyst was 1: 1. These mixtures were used in Examples 8-11, except that the integrated peak areas shown in Table 3 were compared for specific vibrations in the range of 2392-2258 cm ⁻¹ specific for C═O vibrations in carbon dioxide. And subjected to the same test procedure as described.

Examples 14-15
Using the catalyst preparation method C, the two different metal oxides of the present invention are produced in amounts to produce the bimetallic catalyst of the present invention using pre-calcined Mg / Al / HTC and an aqueous solution of two different water soluble metal salts. A bimetallic catalyst was prepared. The HTC used was pre-fired at 550 ° C. for 1 hour and held in a desiccator to avoid interaction with moisture and CO ₂ . The impregnation was carried out using the well-known initial wetting method with selected pairs of nitrates, ammonium salts and / or oxalates of additional metals. The two calcined catalysts were then individually evaluated for performance in a laboratory-level pyrolysis apparatus in the same manner as used in Examples 1-7, under similar test systems and under similar conditions. did.

  The catalyst was utilized under rapid pyrolysis conditions at 515 ° C. using the same biomass used in the experiments described above with reference to FIGS. The material used in this operation was 75% by weight sand and 25% by weight sand as a heat transfer agent supplied with biomass samples in the absence of air, molecular oxygen, molecular hydrogen and liquid solvent or diluent. It was a mixture of Fe / Ca / HTC catalyst. The amount of these materials used was 36 g sand, 12 g Fe / Ca / HTC catalyst and 3 g biomass. This rapid pyrolysis test procedure involved the following operations.

  Table 4 summarizes the characteristics of the product formed with the above rapid pyrolysis procedure compared to the product formed with the same amount of the same HTC without additional catalyst components.

From Table 4 it will be noted that the Fe / Ca / HTC catalyst results in a much greater yield of CO, CO ₂ and oxygen removal compared to the unadded HTC material. It will also be seen that the bio-oil formed by the process has a significantly lower acidity when using Fe / Ca / HTC catalyst.

Additional embodiments of the present invention include:

(BA) A method of producing one or more fluid hydrocarbon products from a biomass material in a solid state, the method comprising:
(I) Under stirring in a pyrolysis reactor (A) Particulate or finely divided solid biomass material that is untreated except for any drying and / or crushing;
(B) when loaded into the reactor, (1) a single pair of metals, (2) a single pair of at least one oxide of each of the metals, or (3) (a) one or both of a single pair of metals. At least one calcined hydrotalcite or hydrotalcite-like compound, layered two impregnated or carrying at least one oxide and (b) at least one free metal of one or both of a single pair of metals A rehydrated, impregnated or doped solid state calcined product comprising, consisting essentially of, or consisting of a hydroxide, anionic clay, or a mixture of two or more thereof. (Wherein the calcined product is in the presence of free oxygen (eg air or oxygen and a small amount selected from nitrogen, neon, argon or krypton). At least one pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anion impregnated with or carrying the metal salt of said pair with a mixture of inert gases) A single pair of metals of (1), (2) or (3) is formed from the following groups: Ca and Ce, Ca and Cu, and Ca. Fe, Ca and Mn, Ca and Y, Ca and Zn, Ce and Fe, Ce and Ni, Ce and Y, Cu and Nb, Fe and Y, Mo and Zn, Mn and Y, Ni and Y); And (C) forming a mixture by contacting a solid state heating medium in a solid state;
(II) in the pyrolysis reactor, excluding (without) the addition of air, molecular oxygen, molecular hydrogen, and / or the addition of a liquid diluent or carrier such as water A method comprising rapidly or instantaneously pyrolyzing at least a portion of said mixture of (I) at one or more temperatures greater than about 500 ° C. thereby forming a fluid pyrolysis product.

  (BB) The single pair of metals of (1), (2) or (3) is Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo And a method such as (BA) selected from Zn and Mn and Y.

  (BC) A method as in (BB), wherein the single pair of metals of (1), (2) or (3) is selected from Ca and Cu and Ca and Fe.

  (BD) The pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof contains magnesium and aluminum metals (BA) to ( BC).

  (BE) The rapid or instantaneous pyrolysis is carried out at a temperature substantially above 500 ° C. to about 650 ° C. at atmospheric pressure, and the biomass material is an inert anhydrous carrier gas, preferably nitrogen, The pyrolysis reactor is loaded together with argon, neon or krypton or a mixture of two or more thereof, the solid particulate heat transfer medium is sand, and the calcined pyrolysis catalyst when loaded into the reactor is Having an average particle size in the range of about 40 to about 400 microns, preferably about 50 to 150 microns, and activated by rehydration when the calcined pyrolysis catalyst is loaded into the pyrolysis reactor. And the process is carried out with a residence time in the pyrolysis reactor of 30 seconds or less, preferably 20 seconds or less, or more preferably 10 seconds or less, as in any of (BA) to (BC) .

  (BF) The method as in any one of (BA) to (BC), wherein the temperature is in the range of about 510 ° C to about 575 ° C.

(CA) Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn,
Impregnated with a salt of a metal pair selected from Ce and Fe, Ce and Ni, Ce and Y, Cu and Nb, Fe and Y, Mo and Zn, Mn and Y, and Ni and Y, preferably an inorganic salt. Free oxygen (eg, air) at one or more elevated temperatures after being dried such that at least a portion of one or both of one or both of the metal pair is doped or doped and is converted to an oxide. Or a mixture of at least one inert gas selected from oxygen and nitrogen, neon, argon or krypton), or at least one pre-calcined hydrotalcite or hydrotalcite-like compound, layered Solid state pyrolysis catalyst comprising, consisting essentially of or consisting of a calcined product formed from a dihydroxide, an anionic clay, or a mixture of two or more thereof Narubutsu.

(CB) The metal pairs are selected from Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo and Zn, and Mn and Y (CA ) Catalyst composition.

  (CC) A catalyst composition such as (CB), wherein the pair of metals is selected from Ca and Cu and Ca and Fe.

  (CD) The pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof contains magnesium and aluminum metals (CA) to ( CC).

  A component referred to by a chemical name or formula anywhere in this specification or claim, whether referred to in the singular or in the plural, is another substance referred to by chemical name or chemical type (e.g., Before they come into contact with other components, solvents, etc.). Which chemical changes, transformations and / or reactions, if any, occur in the resulting mixture or solution are components identified under the conditions under which such transformations and transformations and / or reactions are required according to the present disclosure. It is not a problem because it is the natural result of being together.

  The present invention can include, consist of, or consist essentially of the materials and / or procedures cited herein.

  Except as expressly indicated otherwise, the article “a” or “an” is not intended to be limiting, if used or used herein, and claims It should not be construed as limited to the single element that the article points to. Rather, the article “a” or “an”, as used herein or when used, is intended to cover one or more such elements, unless the text clearly indicates otherwise.

  The present invention is susceptible to considerable changes in practice. Accordingly, the foregoing description is not intended to be limiting and should not be construed to limit the invention to the specific illustrations presented above.

Claims (20)

A method for producing one or more fluid hydrocarbon products from a biomass material in a solid state, the method comprising:
(I) Under stirring in a pyrolysis reactor (A) Particulate or finely divided solid biomass material that is untreated except for any drying and / or crushing;
(B) When loaded into the reactor, (1) a single pair of metals, (2) a single pair of at least one oxide of each of the metals, or (3) (a) one or both of a single pair of metals. At least one calcined hydrotalcite or hydrotalcite-like impregnated or carrying a combination of at least one oxide of (b) and at least one free metal of one or both of a single pair of metals Rehydrated, impregnated or doped solids comprising, consisting essentially of or consisting of compounds, layered dihydroxides, anionic clays, or mixtures of two or more thereof A calcined pyrolysis catalyst in the state, wherein the calcined product is impregnated with or carries the pair of metal salts in the presence of free oxygen (1), (2) or (3) formed by firing the formed hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof. The single pairs of metals are the following groups: Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Ce and Fe, Ce and Ni, Ce and Y, Cu and Nb , Fe and Y, Mo and Zn, Mn and Y, Ni and Y); and (C) forming a mixture by contacting a solid state heating medium in a solid state;
(II) at one or more temperatures above about 500 ° C. in the pyrolysis reactor without the addition of air, molecular oxygen, molecular hydrogen, or liquid diluent or support The method comprising rapidly or instantaneously pyrolyzing at least a portion of the mixture of (I), thereby forming a fluid pyrolysis product.   The single pair of metals of (1), (2) or (3) is Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo and Zn, And the method of claim 1 selected from Mn and Y.   The method of claim 2, wherein the single pair of metals of (1), (2) or (3) is selected from Ca and Cu and Ca and Fe.   The pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof contains magnesium and aluminum metals. The method described in 1.   The rapid or instantaneous pyrolysis is conducted at a temperature substantially above 500 ° C. to about 650 ° C. at atmospheric pressure, and the biomass material is loaded into the pyrolysis reactor with an inert anhydrous carrier gas; The solid state particulate heat medium is sand, the calcined pyrolysis catalyst when loaded into a reactor has an average particle size of about 40 to about 400 microns, and the calcined pyrolysis catalyst comprises 4. When loaded into a pyrolysis reactor, activated by rehydration, and the process is carried out in the pyrolysis reactor with an average residence time of 30 seconds or less. The method described in 1.   The method of any one of claims 1 to 3, wherein the temperature is in the range of about 510 ° C to about 575 ° C. Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Ce and Fe, Ce and Ni, Ce and Y, Cu and Nb, Fe and Y, Mo and Zn, and Mn Y and Ni and Y
Impregnated or doped with a salt of a metal pair selected from and dried so that one or more oxides of at least part of one or both of the metal pairs are converted to oxides At least one pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or two thereof, which is subsequently calcined in the presence of free oxygen at one or more high temperatures A solid state pyrolysis catalyst composition comprising, consisting essentially of, or consisting of a calcined product formed from the above mixture.   8. The pair of metals is selected from Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo and Zn, and Mn and Y. The catalyst composition.   9. The catalyst composition of claim 8, wherein the pair of metals is selected from Ca and Cu and Ca and Fe.   The precalcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof contains magnesium and aluminum metals. The catalyst composition as described in 1. Producing pyrolysis products from untreated particulate or finely divided solid state biomass material except for any drying and / or crushing without the addition of air, molecular oxygen, molecular hydrogen or liquid A method of preparing a catalyst composition adapted to
(A) creating or providing one or more solutions that provide dissolved metal pairs, either individually or collectively, (the solutions may be the same or different; The dissolved metal pairs of the one or more solutions include Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, and Ce and Fe. , Ce and Ni, Ce and Y, Cu and Nb, Fe and Y, Mo and Zn, Mn and Y, and Ni and Y).
(B) Powdered or particulate hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or the like by an initial wetting method using one or more of the solutions of (A) above Impregnating a mixture of two or more of to form a wet mixture, drying the wet mixture to form a product mixture, and then calcining the product mixture in the presence of free oxygen.   12. The metal pair is selected from Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo and Zn, and Mn and Y. the method of.   The method of claim 12, wherein the pair of metals is selected from Ca and Cu and Ca and Fe.   14. The pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof contains magnesium and aluminum metals. The method described in 1.   A method of converting a solid state biomass material into one or more fluid hydrocarbon products, wherein the particulate or finely divided solid state biomass material is untreated except for any drying and / or crushing, 12. Introducing into a pyrolysis reactor operating at a temperature above about 500 ° C. under rapid or instantaneous operating conditions, said reactor as (1) when initially introduced into the reactor Containing a calcined pyrolysis catalyst that was a catalyst composition formed by the described method and (2) a fluidized mixture of solid particulate heat medium, addition of air, addition of molecular oxygen, molecular Said process, which is carried out without the addition of hydrogen and / or the addition of a liquid diluent or carrier.   16. The metal pair is selected from Ca and Ce, Ca and Cu, Ca and Fe, Ca and Mn, Ca and Y, Ca and Zn, Fe and Y, Mo and Zn, and Mn and Y. the method of.   The method of claim 16, wherein the pair of metals is selected from Ca and Cu and Ca and Fe.   18. The pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof contains magnesium and aluminum metals. The method described in 1.   The rapid or instantaneous operating conditions include a temperature substantially above 500 ° C. to about 650 ° C. at atmospheric pressure, and biomass material is loaded into the pyrolysis reactor with an inert anhydrous carrier gas, the solid state When the calcined pyrolysis catalyst is loaded into the pyrolysis reactor, the calcined pyrolysis catalyst has an average particle size of about 40 to 400 microns. 18. When loaded into a reactor, activated by rehydration, and the process is carried out in a pyrolysis reactor with an average residence time of 30 seconds or less. Method.   The pre-calcined hydrotalcite or hydrotalcite-like compound, layered dihydroxide, anionic clay, or a mixture of two or more thereof contains magnesium and aluminum metals, and the rapid or instantaneous operation. The conditions include a temperature substantially above 500 ° C. up to about 650 ° C. at atmospheric pressure, biomass material is loaded into the pyrolysis reactor with an inert anhydrous carrier gas, and the solid state particulate heating medium is sand When the calcined pyrolysis catalyst is loaded into the pyrolysis reactor, having an average particle size of about 40 to 400 microns, and when the calcined pyrolysis catalyst is loaded into the pyrolysis reactor 18. A process according to any of claims 15 to 17, which has been activated by rehydration and the process is carried out in a pyrolysis reactor with an average residence time of not more than 30 seconds.

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